The mass transfer resistance associated with penetrating the mouth of a very small pore is evaluted using classical molecular dynamics simulation techniques. The effects of temperature, pore size, and thermal motion of the adsorbent atoms are studied for a slit pore mouth model. Adsorption followed by surface diffusion to the pore mouth makes a significant contribution to the mass transfer when the temperature is low or, equivalently, when the adsorptive potential is strong. Thermal vibrations of the adsorbent atoms have little effect on the adsorption/surface diffusion mechanisms but cause fluctuations in the effective pore mouth area which can significantly affect transport rates. Perhaps the most important observation is that when the pore size approaches the kinetic diameter of the gas molecules, changes of a few percent in the pore size cause order-of-magnitude changes in the resistance. Therefore, it is possible that the surface barrier effect observed in zeolites and carbon molecular sieves is governed by highly localized (single atomic layer) structural details.